The invention stated herewith, is a new process for the extraction and concentration of unsaponifiable substances, containing liposoluble vitamins and provitamins, growth factors and animal and vegetable hormones, called from this point out as xe2x80x9cvaluable productsxe2x80x9d, obtained from animal or vegetable products, or even from the residues of the industrialization of these same products, without the need for solvents. The objective here is the extraction and concentration of the xe2x80x9cvaluable productsxe2x80x9d, by means of high vacuum distillation/evaporation, also producing fatty acids and other high quality organic acids, by hydrolyzing the residues obtained from distillation/evaporation.
The novelty of this new invention process lies in the fact that while the processes used nowadays, to separate and concentrate xe2x80x9cvaluable productsxe2x80x9d, use solvents, taking advantage of the difference of solubility between unsaponifiable substances and their soap matrix, this new process uses, by means of high vacuum distillation/evaporation, the difference of volatility between volatile unsaponifiables and fatty acid, rosin acid and other practically non-volatile organic acid soaps, under the same conditions.
The solvents available at present are not sufficiently selective to obtain, though the current process, a reasonable separation between the unsaponifiable components and the fatty acids, the rosin acid soaps, etc. Due to this, many times it is necessary to use more than one solvent, which in turn complicates and increases tremendously the cost of recovery and recycling of the same.
In the case of extraction by distillation, the difference between the boiling point of volatile products, such as unsaponifiable components, and the boiling point of different organic acid soaps is so remarkable, that separation is possible at a high level of efficiency. Prior to the invention of this new process, the problem was the very high melting point, close to the decomposition temperature of sodium or potassium, fatty acid, rosin acid soaps, etc. Even when melted, these soaps form extremely viscous liquids, which make industrial handling difficult. While at the high temperature necessary to maintain their flow, around 200xc2x0 C., these soaps are in permanent decomposition, compromising the extraction output and the quality of the final product.
This new process has solved this problem, transforming sodium or potassium soaps, obtained from the saponification of animal or vegetable oils and fats processing, and from the saponification of the residues obtained in the industrialization of the same; rich in unsaponifiables where xe2x80x9cvaluable productsxe2x80x9d can be found; into metallic soaps, which have a lower melting point, and when melted, have low enough viscosity to help handling during the distillation/evaporation process.
The recovery of the unsaponifiable fraction of the residues from the industrialization of animal or vegetable products, is of great commercial interest, due to the fact that, in many cases, the xe2x80x9cvaluable productsxe2x80x9d have vitamin activities such as: tocopherols (vitamin E), tocotrienols, carotenoids, vitamin A, vitamin K, vitamin D, while the same products present cholesterol reducing properties such as: sterols, tocotrienols; as well as anticarcinogenic properties such as: tocotrienols, sterols, lycopene, alphacarotene; and some other products which can be used as a chemical synthesis structure, like for example: sterols for human hormone synthesis, vitamin D synthesis; and even other products which have nutraceutical properties. There is also commercial interest in some products, which present emulsifying properties, emulsion stabilizers and/or viscosity modifiers, such as sterols, in their cosmetic formulas.
The currently known processes for the extraction and concentration of unsaponifiable substances, containing liposoluble vitamins and provitamins, growth factors and vegetable hormones from the residue of industrialized animal or vegetable products, or rather xe2x80x9cvaluable productsxe2x80x9d, use solvents or solvent mixtures in very large proportions, when compared to the quantity of the material submitted for extraction. These solvents are specific, thus making the process very expensive. Furthermore, the solvents need additional processes for their removal and/or recycling in the extraction and pre-concentration process of the xe2x80x9cvaluable productsxe2x80x9d, consequently, making these processes harder and more expensive, resulting in a scarce and expensive final product.
Contrary to all the already known processes for the separation and concentration of unsaponifiables, containing the xe2x80x9cvaluable productsxe2x80x9d, mentioned above, the process presented in this paper, uses no solvents. The process presented herewith, is based on the following steps:
(A) Pre-treatment of the material containing the xe2x80x9cvaluable productsxe2x80x9d through saponification with a strong-base material. Partial or complete saponification with the strong-base material is carried out by hydroxides, such as sodium and potassium.
(B) Partial or total transformation of a strong-base soap into a metallic soap with a lower melting point, is accomplished through the reaction of oxides, sulfates, hydroxides, carbonates, chlorides, etc., with metals such as zinc, iron, manganese, magnesium, calcium, aluminum, etc. or other metals that form fluid soaps at temperatures below 180xc2x0 C. This reaction is carried out directly, by allowing the metal oxide to react with the fatty acid, rosin acid, or any organic acid; or even by double exchange with sulfates or chlorides, transforming sodium and potassium soaps into metallic soaps with lower melting points, thus facilitating industrial handling as well as drying, etc., thus avoiding its degradation during the industrial process.
(C) Drying of the soap through the elimination of water and some volatile substances in the material previously saponified by vacuum distillation/evaporation.
(D) Separation and concentration of the unsaponifiables, contained in low melting point metallic soaps, by means of high vacuum distillation/evaporation, whether by falling film evaporator or by short path evaporation, in temperatures ranging from 100 to 300xc2x0 C., and by absolute pressure of 5 to 1xc3x9710xe2x88x923 mbar or below. This distillation/evaporation is carried out in one or more stages, according to the desired degree of concentration or even when fractionation of the unsaponifiable part is required.
(E) Fraction concentration rich in unsaponifiables, by re-vaporation of the material at high vacuum, separating it from light and heavy fractions.
(F) The residue of the distilled unsaponifiables is hydrolyzed using diluted sulfuric acid or hydrochloric acid, in order to obtain fatty acids, rosin acids and other organic acids, presenting low levels of light components and of unsaponifiable materials.
The unsaponifiable sources used in this process are animal or vegetable oils and fats, by-products of the industrialization of the same, or residues from the products of paper and cellulose industry, such as: Tall oil, obtained from the soap of wood processing, for the production of cellulose (xe2x80x9cTall oil black liquor soap skimmingxe2x80x9d), or the soap itself obtained from cellulose processing, the xe2x80x9cTall oil pitchxe2x80x9d (residue from xe2x80x9ctall oilxe2x80x9d distillation); Sugarcane oil; residues from extraction; degumming, and refining of oils and fats, such as: lecithins, neutralization soap stock, deodorization distillates and physical refining, xe2x80x9chot wellxe2x80x9d soap stocks, and winterization residues; distillation residues of fatty acids and esters (ethyl, methyl, butyl); coffee oil, fish oil, cod liver oil; animal or vegetable oils and fats rich in unsaponifiable materials, such as: wheat germ oil, corn germ oil, palm oils, andiroba oils, oil from tomato residues and other residues.
The increase in fluidity and decrease of the melting point of viscous materials, like the residue of xe2x80x9cTall oilxe2x80x9d (pitch) distillation, can be obtained by blending it with other unsaponifiable residues, before or after the saponification of the Tall oil (pitch) distillation residue, and residues such as vegetable oil neutralization soapstock, Tall oil black liquor soap skimming or other residues or products, which after soap formation, become fluid at a temperature below 200xc2x0 C. Thus, obtaining better results and better efficiency in the process.
The presence of glycerides (di- or triglycerides) or sucrose-polyesters contribute to decrease the melting point and increase the fluidity of some materials like xe2x80x9cTall oil pitchxe2x80x9d soap (Tall oil distillation residue), which could contribute to the process yield. These additives, however, are not essential to the separation process of the unsaponifiables described herewith.
The residues hydrolyzed by diluted sulfuric acid or hydrochloric acid, which are the result of the process described in this patent report, usually come from Tall oil distillation residues, neutralization soapstock residues, animal or vegetable oil and fat deodorization residues, and animal and vegetable oils containing unsaponifiables.
The following tables have the objective of clarifying the process and the examples given.
Table 1 shows the melting points of the zinc, iron and magnesium soaps, and the blends with dry sodium soap from cellulose production xe2x80x9cblack liquor soap skimmingxe2x80x9d (BLSS).
Table 2 shows the characteristics of the xe2x80x9ctall oilxe2x80x9d obtained from hydrolyzed BLSS magnesium soap residue after short path evaporation.
As shown in the results presented in table 1, the transformation of BLSS sodium soap into Zn, Mg, or Fe soaps, decreases the melting point, significantly. The mixture of sodium or potassium soaps with Zn, Mg, Fe soaps, either formed by partial transformation of sodium soaps, or by their blending, also decreases the melting point.
Next, some examples of extraction and concentration of unsaponifiable substances, containing lyposoluble vitamins and provitamins, growth factors, and vegetable hormones from residues of industrialized animal and vegetable products. In other words, the extraction and concentration process of the xe2x80x9cvaluable productsxe2x80x9d, without the use of solvents obtained through the process presented in this report, will be described.